US11780987B2 - Light-blocking member, black resin composition, and black resin molded article - Google Patents

Light-blocking member, black resin composition, and black resin molded article Download PDF

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US11780987B2
US11780987B2 US15/573,604 US201615573604A US11780987B2 US 11780987 B2 US11780987 B2 US 11780987B2 US 201615573604 A US201615573604 A US 201615573604A US 11780987 B2 US11780987 B2 US 11780987B2
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light
blocking
black pigment
blocking member
black
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US20180134862A1 (en
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Tsuyoshi NAGAHAMA
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Kimoto Co Ltd
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Kimoto Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0018—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means for preventing ghost images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/003—Light absorbing elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present invention relates to a light-blocking member, a black resin composition, and a black resin molded article.
  • the inner wall surfaces of a camera, and the like are composed of members having light-blocking properties to prevent the occurrence of halation and ghosts due to outside light, and the like.
  • a light-blocking member for example, a light-absorbing member in which a light-absorbing film comprising a black paint containing carbon black and having a predetermined surface shape is provided on a surface of a substrate film is known (see Patent Literature 1).
  • members having light-blocking properties are used in the shutters, diaphragm members, lens units, and the like of various optical apparatuses such as single-lens reflex cameras, compact cameras, and video cameras. Further, in these light-blocking members, excellent slip properties (sliding properties) and low gloss are also needed because of their modes of use.
  • metal thin films to which black paints are applied have been used as the shutters, diaphragm members, lens units, and the like of various optical apparatuses.
  • replacement by lightweight plastic materials has been studied.
  • a light-blocking member in which light-blocking membranes containing carbon black and a lubricant in a thermosetting resin or a room temperature curable resin are formed on both surfaces of a resin film is known (see Patent Literature 2).
  • a light-blocking membrane in which light-blocking membranes containing carbon black, a lubricant such as polyethylene wax, silica fine particles having an amount of oil absorbed of 250 (g/100 g) or more, and a binder resin are formed on both surfaces of a resin film is also known (see Patent Literature 3).
  • a light-blocking filler such as carbon black should be highly filled.
  • the total filling rate of fillers such as carbon black, a lubricant, and silica fine particles is already in a saturated state, and more highly filling the fillers reaches a technical limit. Therefore, when the optical density per predetermined thickness is increased, a search for a new design guide that replaces the conventional formulation design in which the filling ratio of carbon black is increased is needed.
  • the present invention has been made in view of the above problem. Specifically, it is an object of the present invention to provide a light-blocking member, a black resin composition, and a black resin molded article in which the optical density per predetermined thickness is increased.
  • the present inventors have studied diligently in order to solve the above problem. As a result, the present inventors have found that the above problem is solved by using two large and small black pigments as light-blocking fillers, arriving at the present invention.
  • the present invention provides specific embodiments shown in the following (1) to (13).
  • a light-blocking member comprising a substrate; and a light-blocking membrane (film) provided on at least one surface of the substrate, wherein
  • the light-blocking membrane contains at least a binder resin and a black pigment
  • the black pigment contains a first black pigment having an average particle diameter D 50 of 0.4 to 2.5 ⁇ m and a second black pigment having an average particle diameter D 50 smaller than the average particle diameter D 50 of the first black pigment.
  • an optical density of the light-blocking membrane is 0.54 to 2.00 ( ⁇ m ⁇ 1 ) in terms of thickness.
  • the average particle diameter D 50 of the second black pigment is 0.01 to 0.3 ⁇ m.
  • the black pigment is contained in an amount of 10% by mass or more and 60% by mass or less in terms of solids based on all resin components contained in the light-blocking membrane.
  • the light-blocking membrane has a total thickness of 3 ⁇ m or more and less than 10 ⁇ m.
  • the binder resin comprises at least one selected from a group consisting of a thermoplastic resin, a thermosetting resin, a thermoplastic elastomer, a thermosetting elastomer, an ultraviolet curable resin, and an electron beam curable resin.
  • the substrate is a sheet-shaped substrate
  • the light-blocking membranes are provided on one major surface and the other major surface of the sheet-shaped substrate.
  • a black resin composition comprising at least a matrix resin and a black pigment dispersed in the matrix resin, wherein
  • the black pigment contains a first black pigment having an average particle diameter D 50 of 0.4 to 2.5 ⁇ m and a second black pigment having an average particle diameter D 50 smaller than the average particle diameter D 50 of the first black pigment.
  • an optical density in terms of thickness when the black resin composition is molded is 0.54 to 2.00 ( ⁇ m ⁇ 1 ).
  • the average particle diameter D 50 of the second black pigment is 0.01 to 0.3 ⁇ m.
  • the black pigment is contained in an amount of 10% by mass or more and 60% by mass or less in terms of solids based on all resin components.
  • the matrix resin comprises at least one selected from a group consisting of a thermoplastic resin, a thermosetting resin, a thermoplastic elastomer, a thermosetting elastomer, an ultraviolet curable resin, and an electron beam curable resin.
  • the optical density per predetermined thickness (ODt) is especially improved.
  • the reason is not certain but is presumed to be that the voids between the particles of the first black pigment are filled with the second black pigment having a small average particle diameter D 50 , and thus the particles of the black pigments are densely filled compared with the conventional design.
  • the action is not limited to this. From the above features of the present invention, at least the following superiority is derived.
  • the optical density per predetermined thickness (ODt) is not sufficient in the conventional art, and therefore further miniaturization and/or film thinning cannot be pursued. This is due to the fact that the light-blocking properties as basic performance are not sufficient.
  • the optical density per predetermined thickness (ODt) is especially improved, and therefore miniaturization and/or film thinning and high light-blocking properties can be balanced at a high level.
  • a light-blocking filler such as carbon black must be relatively highly blended in the conventional art.
  • the filling rate needs to be increased to a saturated state.
  • the process margin during manufacture is also narrow.
  • a mode in which the amount of the black pigments blended is relatively small can be realized. It can also be said that in the mode in which the amount of the black pigments blended is relatively small in this manner, design flexibility for further improvement is sufficiently ensured. For example, a design change such as blending large amounts of other additives can be sufficiently made considering other required performance.
  • the amount of fillers such as black pigments blended is relatively small, the dispersibility, the film-forming properties, and the handling properties are excellent, and the process margin during manufacture can be increased.
  • a light-blocking member and the like not only having excellent light-blocking properties as described above but having low surface glossiness (excellent delustering properties) and excellent slip properties (sliding properties) can also be realized.
  • This is presumed to be due to the fact that by blending the two large and small black pigments having different average particle diameters D 50 in the resin, fine irregularities formed by the black pigment having a small average particle diameter D 50 are superimposed on irregularities in the surface formed by the black pigment having a large average particle diameter D 50 , and as a result the reflection of incident light decreases more.
  • the glossiness (specular glossiness) of the surface decreases, and good delustering properties are exhibited when the light-blocking member is formed, and further, good sliding properties are obtained.
  • the action is not limited to this.
  • the amount of carbon black blended, the amount of the matting agent blended, and the amount of the slipping agent blended are finely adjusted. This is because three types of performance, light-blocking properties, surface glossiness, and slip properties, are in a trade-off relationship. Specifically, by highly blending a filler such as carbon black, the slip properties can be increased, but at the same time the surface glossiness increases.
  • a method of blending a matting agent (delusterant) in order to decrease surface glossiness is also known, but in this case, the slip properties tend to deteriorate, and further, due to decreases in the amounts of carbon black and the like blended, even light-blocking properties can be sacrificed.
  • blending a slipping agent in order to increase slip properties is also attempted, but since the total filling rate of the fillers described above is already in the saturated state, the amounts of other fillers such as carbon black blended need to be decreased for the blending of the slipping agent, and in this case, light-blocking properties as basic performance are sacrificed.
  • the present invention has special technical significance in newly finding a novel formulation design that can eliminate the technical trade-off relationship, which cannot be eliminated by the conventional formulation design.
  • a light-blocking member, a black resin composition, and a black resin molded article in which the optical density per predetermined thickness (ODt) is increased, and the like can be provided.
  • a light-blocking member that adapts to further miniaturization and/or film thinning while having light-blocking properties equal to or more than those of the conventional art can be realized.
  • a light-blocking member and the like not only having excellent light-blocking properties but having low surface glossiness and also excellent slip properties can also be realized.
  • the dispersibility, film-forming properties, and handling properties during manufacture can be improved.
  • FIG. 1 is a diagram schematically showing the main part of a light-blocking member 1 in a first embodiment.
  • FIG. 1 is a diagram schematically showing the main part of a light-blocking member 1 in the first embodiment of the present invention.
  • the light-blocking member 1 in this embodiment comprises a substrate 2 and a light-blocking membrane 3 (a light-blocking film 3 ) provided on at least one surface of this substrate 2 .
  • the light-blocking membrane 3 contains at least a binder resin 31 and two black pigments 32 and 33 having different average particle diameters D 50 .
  • the components of the light-blocking member 1 will be described in detail below.
  • the type of the substrate 2 is not particularly limited as long as it can support the light-blocking membrane 3 .
  • Specific examples of the substrate 2 include, but are not particularly limited to, paper, synthetic paper, metal sheets, alloy sheets, metal foil, synthetic resin films, and laminates thereof.
  • the substrate 2 may or may not have adhesiveness to the light-blocking membrane 3 .
  • the substrate 2 having no adhesiveness to the light-blocking membrane 3 can be allowed to function as a release film.
  • synthetic resin films are preferably used.
  • the synthetic resin films include polyester films, ABS (acrylonitrile-butadiene-styrene) films, polyimide films, polystyrene films, and polycarbonate films.
  • Acrylic, polyolefin-based, cellulosic, polysulfone-based, polyphenylene sulfide-based, polyethersulfone-based, and polyetheretherketone-based films can also be used.
  • polyester films are preferably used.
  • stretched, particularly biaxially stretched, polyester films have excellent mechanical strength and dimensional stability and therefore are particularly preferred.
  • polyimide films are particularly preferred.
  • the appearance of the substrate 2 may be any of transparent, semitransparent, and opaque appearance and is not particularly limited.
  • foamed synthetic resin films such as foamed polyester films, and synthetic resin films in which black pigments such as carbon black and other pigments are contained can also be used.
  • the optical density of the entire light-blocking member 1 can also be reinforced by using the substrate 2 having high optical density.
  • the thickness of the substrate 2 can be appropriately set according to the required performance and the application and is not particularly limited. Generally, 1 ⁇ m or more and less than 250 ⁇ m is considered as a rough standard. Here, from the viewpoint of the strength and rigidity of the light-blocking member 1 , and the like, 51 ⁇ m or more and less than 250 ⁇ m is preferred, and from the viewpoint of weight reduction and film thinning, 1 ⁇ m or more and 50 ⁇ m or less is preferred.
  • the optical density in terms of thickness (ODt) of the light-blocking membrane 3 is especially increased, and therefore the light-blocking member 1 having, for example, a total thickness of 60 ⁇ m or less, preferably a total thickness of 35 ⁇ m or less, further preferably a total thickness of 15 ⁇ m or less, and particularly preferably a total thickness of 10 ⁇ m or less can be realized while various types of performance such as light-blocking properties are maintained even if both the substrate 2 and the light-blocking membrane 3 are set as thin films.
  • the thickness of the substrate 2 is more preferably 1 ⁇ m or more and 25 ⁇ m or less, further preferably 4 ⁇ m or more and 10 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 7 ⁇ m or less.
  • the surface of the substrate 2 can also be subjected to various known surface treatments such as anchor treatment and corona treatment as needed.
  • the light-blocking membrane 3 is provided on at least one surface of the above-described substrate 2 and contains at least the binder resin 31 and the black pigments 32 and 33 .
  • FIG. 1 a mode in which the light-blocking membrane 3 is provided on only one major surface (upper surface) of the sheet-shaped substrate 2 is shown, but the light-blocking membranes 3 may be provided on one major surface (upper surface) of and the other major surface (lower surface) of the sheet-shaped substrate 2 respectively.
  • binder resin 31 used here examples include, but are not particularly limited to, thermoplastic resins or thermosetting resins such as poly(meth)acrylic acid-based resins, polyester-based resins, polyvinyl acetate-based resins, polyvinyl chloride-based resins, polyvinyl butyral-based resins, cellulosic resins, polystyrene/polybutadiene resins, polyurethane-based resins, alkyd resins, acrylic resins, unsaturated polyester-based resins, epoxy ester-based resins, epoxy-based resins, epoxy acrylate-based resins, urethane acrylate-based resins, polyester acrylate-based resins, polyether acrylate-based resins, phenolic resins, melamine-based resins, urea-based resins, and diallyl phthalate-based resins.
  • thermoplastic resins or thermosetting resins such as poly(meth)acrylic acid-based resins, polyester-based resins, poly
  • thermosetting elastomers ultraviolet curable resins, electron beam curable resins, and the like can also be used. One of these can be used alone, and two or more of these can also be used in combination.
  • the binder resin can be appropriately selected and used according to the required performance and the application. For example, in applications where heat resistance is required, thermosetting resins are preferred.
  • the content of the binder resin 31 in the light-blocking membrane 3 is not particularly limited but is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and further preferably 60 to 80% by mass in terms of solids based on the total amount of the light-blocking membrane 3 .
  • physical properties such as the adhesiveness between the substrate 1 and the light-blocking membrane 3 and the light-blocking properties, sliding properties, and delustering properties of the light-blocking membrane 3 can be balanced at a high level.
  • a mode in which the amount of the black pigments blended is relatively small can be realized as described later, and therefore the content of the binder resin 31 can be relatively more increased (for example, 65% by mass or more) than in the conventional art, which as a result can contribute to the improvement of the dispersibility of the black pigments, the film-forming properties, handling properties, adhesiveness, slip properties, and abrasion resistance of the light-blocking membrane 3 , and the like.
  • the black pigments 32 and 33 contained in the light-blocking membrane 3 color the binder resin 31 black to provide light-blocking properties.
  • the black pigments 32 and 33 contained in the light-blocking membrane 3 two black pigments having different average particle diameters D 50 , that is, a first black pigment 32 having an average particle diameter D 50 of 0.4 to 2.5 ⁇ m and a second black pigment 33 having an average particle diameter D 50 smaller than the average particle diameter D 50 of this first black pigment, are used.
  • black pigments used here include, but are not particularly limited to, black resin particles, titanium black, magnetite-based black, copper-iron-manganese-based black, titanium black, and carbon black.
  • black resin particles, titanium black, and carbon black are preferred because of excellent concealing properties, and carbon black is more preferred.
  • carbon black conductive carbon black is particularly preferably used from the viewpoint of providing conductivity to the light-blocking membrane 3 to prevent electrostatic charging.
  • carbon black The history of carbon black is old, and various grades of carbon black simple substances and carbon black dispersions are commercially available from, for example, Mitsubishi Chemical Corporation, Asahi Carbon Co., Ltd., MIKUNI COLOR LTD., RESINO COLOR INDUSTRY CO., LTD., Cabot, and DEGUSSA.
  • the carbon black should be appropriately selected from among these according to the required performance and the application.
  • the first black pigment 32 has an average particle diameter D 50 of 0.4 to 2.5 ⁇ m
  • the second black pigment 33 has an average particle diameter D 50 smaller than the first black pigment 32 .
  • the average particle diameter D 50 of the first black pigment 32 is more preferably 0.5 to 1.5 ⁇ m from the viewpoint of keeping surface glossiness low, improving slip properties, and the like.
  • the average particle diameter D 50 of the second black pigment 33 is preferably 0.01 to 0.3 ⁇ m, more preferably 0.08 to 0.2 ⁇ m, from the viewpoint of obtaining dispersibility and sufficient light-blocking properties, and the like.
  • the average particle diameter herein means a median diameter (D 50 ) measured by a laser diffraction particle size distribution measuring apparatus (for example, SHIMADZU CORPORATION: SALD-7000).
  • the content of the first black pigment 32 and the second black pigment 33 is not particularly limited but is preferably 20:80 to 95:5, more preferably 30:70 to 80:20, and further preferably 40:60 to 70:30 in a mass ratio in terms of solids from the viewpoint of the balance of light-blocking properties, surface glossiness, and slip properties.
  • the light-blocking membrane 3 may contain a black pigment other than the above-described first and second black pigments 32 and 33 .
  • the content of all black pigments in the light-blocking membrane 3 is not particularly limited but is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 50% by mass or less, and further preferably 20% by mass or more and 40% by mass or less in terms of solids based on all resin components contained in the light-blocking membrane 3 (phr) from the viewpoint of dispersibility, the film-forming properties, handling properties, adhesiveness, slip properties, delustering properties, and abrasion resistance of the light-blocking membrane 3 , and the like.
  • the thickness of the light-blocking membrane 3 can be appropriately set according to the required performance and the application and is not particularly limited. In applications where thickness is allowed, the thickness of the light-blocking membrane 3 should be sufficient, and thus the light-blocking membrane 3 in which the content of all black pigments in the light-blocking membrane 3 is significantly reduced can be realized. In such applications, the total thickness of the light-blocking membrane 3 is preferably 10 ⁇ m or more and 60 ⁇ m or less, more preferably 10 ⁇ m or more and 40 m or less.
  • the total thickness of the light-blocking membrane 3 is preferably 3 ⁇ m or more and less than 10 ⁇ m, more preferably 4 ⁇ m or more and 9 ⁇ m or less, and further preferably 5 ⁇ m or more and 8 ⁇ m or less.
  • the light-blocking membrane 3 in this embodiment has a very high optical density in terms of thickness (ODt) compared with that of conventional ones, and therefore film thinning, which is conventionally difficult, can be realized while optical density equal to or more than that of conventional ones is maintained.
  • the total thickness of the light-blocking membrane 3 means, when the light-blocking membrane 3 is provided on only one major surface of the substrate 2 , the thickness of the light-blocking membrane 3 and means, when the light-blocking membranes 3 are provided on both surfaces (one major surface and the other major surface) of the substrate 2 , a value obtained by adding the thicknesses of the light-blocking membranes 3 on both surfaces.
  • the light-blocking membrane 3 preferably has an optical density in terms of thickness (ODt) of 0.54 to 2.00 ( ⁇ m ⁇ 1 ), more preferably 0.55 to 2.00 ( ⁇ m ⁇ 1 ), further preferably 0.80 to 1.80 ( ⁇ m ⁇ 1 ), particularly preferably 0.90 to 1.50 ( ⁇ m ⁇ 1 ), especially preferably 0.91 to 1.40 ( ⁇ m ⁇ 1 ), and most preferably 0.92 to 1.20 ( ⁇ m ⁇ 1 ).
  • ODt optical density in terms of thickness
  • the light-blocking membrane 3 preferably has a surface glossiness of 5.0% or less.
  • the surface glossiness of the light-blocking membrane 3 is more preferably 4.0% or less.
  • the light-blocking membrane 3 may contain a lubricant in addition to the binder resin 31 and the first and second black pigments 32 and 33 described above.
  • a lubricant By containing the lubricant, the slip properties (sliding properties) of the surface of the light-blocking membrane 3 improve, and the frictional resistance during operation decreases when it is processed into the shutter, diaphragm member, lens unit, or the like of an optical apparatus, and the abrasion resistance of the surface can be improved.
  • this lubricant organic lubricants and inorganic lubricants known as known particulate lubricants can be used. Among these, liquid lubricants are preferred.
  • hydrocarbon-based lubricants such as polyethylene, paraffins, and waxes
  • fatty acid-based lubricants such as stearic acid and 12-hydroxystearic acid
  • amide-based lubricants such as stearic acid amide, oleic acid amide, and erucic acid amide
  • ester-based lubricants such as butyl stearate and monoglyceryl stearate
  • alcohol-based lubricants solid lubricants such as metal soaps, talc, and molybdenum disulfide
  • silicone resin particles polytetrafluoroethylene waxes, fluororesin particles such as polyvinylidene fluoride; crosslinked polymethyl methacrylate particles, and crosslinked polystyrene particles.
  • particularly organic lubricants are preferably used. One of these can be used alone, and two or more of these can also be used in combination.
  • the content of the lubricant is not particularly limited but is generally preferably 0.5 to 10% by mass in terms of solids based on all resin components contained in the light-blocking membrane 3 .
  • the fact that the light-blocking membrane 3 comprises substantially no lubricant is also one of preferred modes.
  • the relative content of the binder resin 31 and the black pigments 32 and 33 in the light-blocking membrane 3 can be increased. This can suppress decreases in light-blocking properties and conductivity and slip properties and further can also contribute to the improvement of the adhesiveness, abrasion resistance, and the like of the light-blocking membrane 3 .
  • Comprising substantially no lubricant means that the content of the lubricant is less than 0.5% by mass in terms of solids based on all resin components contained in the light-blocking membrane 3 , and the content of the lubricant is more preferably less than 0.1% by mass.
  • the light-blocking membrane 3 may contain a matting agent (delusterant). By containing the matting agent, the glossiness (specular glossiness) of the surface of the light-blocking membrane 3 can be decreased, and the light-blocking properties can be improved.
  • this matting agent known ones can be used. Specific examples include, but are not particularly limited to, organic fine particles such as crosslinked acrylic beads, and inorganic fine particles such as silica, magnesium aluminometasilicate, and titanium oxide. Among these, silica is preferred from the viewpoint of dispersibility, cost, and the like. One of these can be used alone, and two or more of these can also be used in combination.
  • the content of the matting agent is not particularly limited but is generally preferably 0.5 to 20% by mass in terms of solids based on all resin components contained in the light-blocking membrane 3 .
  • the fact that the light-blocking membrane 3 comprises substantially no matting agent is also one of preferred modes. Providing a matting-agent-less mode in this manner can increase the relative content of the binder resin 31 and the black pigments 32 and 33 in the light-blocking membrane 3 , can suppress decreases in light-blocking properties and conductivity and slip properties, and further can also contribute to the improvement of the adhesiveness, abrasion resistance, and the like of the light-blocking membrane 3 .
  • Comprising substantially no matting agent means that the content of the matting agent is less than 0.5% by mass in terms of solids based on all resin components contained in the light-blocking membrane 3 , and the content of the matting agent is more preferably less than 0.1% by mass.
  • the light-blocking membrane 3 may further contain other components.
  • these other components include, but are not particularly limited to, conductive agents such as SnO 2 , flame retardants, antimicrobial agents, fungicides, antioxidants, plasticizers, leveling agents, flow-adjusting agents, antifoaming agents, and dispersing agents.
  • conductive agents such as SnO 2
  • flame retardants such as SnO 2
  • antimicrobial agents such as fungicides, antioxidants, plasticizers
  • leveling agents such as SnO 2
  • flow-adjusting agents antifoaming agents
  • dispersing agents such as n-butylamine, triethylamine, or tri-n-butylphosphine
  • an ultraviolet absorbing agent may be used.
  • the method for manufacturing the light-blocking member 1 in this embodiment is not particularly limited as long as the light-blocking member having the above-described configuration and composition is obtained. From the viewpoint of manufacturing the light-blocking member 1 with good reproducibility, simply, and at low cost, conventionally known application methods such as doctor coating, dip coating, roll coating, bar coating, die coating, blade coating, air knife coating, kiss coating, spray coating, and spin coating are preferably used.
  • the light-blocking member 1 in this embodiment can be obtained by applying an application liquid for a light-blocking membrane, which contains, in a solvent, the binder resin 31 the first and second black pigments 32 and 33 described above, and optional components (a lubricant, a matting agent, other components, and the like) blended as needed, to one surface or both surfaces of the substrate 2 , drying the application liquid, and then performing heat treatment, pressurization treatment, and the like as needed, to form the light-blocking membrane 3 on the substrate 2 .
  • an application liquid for a light-blocking membrane which contains, in a solvent, the binder resin 31 the first and second black pigments 32 and 33 described above, and optional components (a lubricant, a matting agent, other components, and the like) blended as needed, to one surface or both surfaces of the substrate 2 , drying the application liquid, and then performing heat treatment, pressurization treatment, and the like as needed, to form the light-blocking membrane 3 on the substrate 2 .
  • solvent of the application liquid used here water; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ether-based solvents such as methyl cellosolve and ethyl cellosolve; alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, and mixed solvents thereof, and the like can be used.
  • ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
  • ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate
  • ether-based solvents such as methyl cellosolve and ethyl cellosolve
  • alcohol-based solvents such as methyl
  • the surface of the substrate 2 can also be subjected to anchor treatment, corona treatment, and the like as needed.
  • an intermediate layer such as an adhesion layer can also be provided between the substrate 2 and the light-blocking membrane 3 as needed.
  • the light-blocking member 1 in this embodiment preferably has an optical density (OD) of 5.4 to 6.0, more preferably 5.5 to 6.0, from the viewpoint of being adaptable to further film thinning and having sufficient light-blocking properties.
  • OD optical density
  • the optical density (OD) is a value measured under conditions described in Examples described later.
  • the optical density per predetermined thickness (ODt) is especially improved, and therefore the light-blocking member 1 in this embodiment can adapt to further miniaturization and/or film thinning without the light-blocking properties being excessively impaired. Therefore, the light-blocking member 1 in this embodiment can be preferably used as a high-performance light-blocking member in the precision machine field, the semiconductor field, the optical apparatus field, and the like where lightness, thinness, shortness, and smallness are required.
  • the light-blocking member 1 in this embodiment can be especially preferably used as a light-blocking member for an optical apparatus such as a high-performance single-lens reflex camera, a compact camera, a video camera, a cellular phone, or a projector, for example, a shutter or a diaphragm member such as a shutter, a diaphragm member, or a lens unit.
  • an optical apparatus such as a high-performance single-lens reflex camera, a compact camera, a video camera, a cellular phone, or a projector, for example, a shutter or a diaphragm member such as a shutter, a diaphragm member, or a lens unit.
  • the present invention can also be carried out in a mode in which the substrate 2 is omitted.
  • the present invention can be effectively carried out as a resin composition (black resin composition) containing at least a matrix resin and a black pigment dispersed in this matrix resin, the resin composition containing as the black pigment a first black pigment having an average particle diameter D 50 of 0.4 to 2.5 ⁇ m and a second black pigment having an average particle diameter D 50 smaller than the average particle diameter D 50 of this first black pigment.
  • the matrix resin used here the same as those described for the binder resin 31 in the above first embodiment can be used.
  • This black resin composition has the same composition as the light-blocking membrane 3 described in the above embodiment, and therefore an optical density in terms of thickness of 0.54 to 2.00 ( ⁇ m ⁇ 1 ) when the black resin composition is molded can be realized. Therefore, by molding the black resin composition by various known molding methods such as heat molding, compression molding, injection molding, blow molding, transfer molding, and extrusion molding, a molded article (black resin molded article) in which the optical density per predetermined thickness (ODt) is especially improved can be obtained. After the black resin composition is once molded into a sheet shape, vacuum forming, pressure forming, or the like can also be performed.
  • Parts indicates “parts by mass” and “phr” indicates “% by mass in terms of solids based on all resin components” contained in a light-blocking membrane unless otherwise noted below.
  • the application liquid for a light-blocking membrane E 1 set forth below was applied to each of both surfaces of a polyester film having a thickness of 6 ⁇ m (K200: Mitsubishi Polyester Film Corporation) as a substrate by a bar coating method so that the thickness after drying was 3 ⁇ m, and dried to form a light-blocking membrane having a thickness of 3 ⁇ m on each of both surfaces of the substrate to fabricate a light-blocking member for an optical apparatus in Example 1.
  • Acrylic polyol 100 parts by mass (ACRYDIC A801P: manufactured by Dainippon Ink and Chemicals, Incorporated, solids: 50%) Isocyanate 25.0 parts by mass (TAKENATE D110N: manufactured by Mitsui Chemicals Polyurethanes, Inc., solids: 60%)
  • First black pigment 20.1 phr (Conductive carbon black SD-TT2003: manufactured by RESINO COLOR INDUSTRY CO., LTD., average particle diameter 0.6 ⁇ m)
  • Second black pigment 19.9 phr (Conductive carbon black #273: manufactured by MIKUNI COLOR LTD., average particle diameter 0.15 ⁇ m)
  • Example 1 Operation was performed as in Example 1 except that the application liquid for a light-blocking membrane RE 1 set forth below was used instead of the application liquid for a light-blocking membrane E 1 , applied so that the thickness after drying was 5 ⁇ m, and dried.
  • a light-blocking member for an optical apparatus in Reference Example 1 was fabricated.
  • Example 1 Operation was performed as in Example 1 except using an application liquid for a light-blocking membrane CE 1 in which in the application liquid for a light-blocking membrane E 1 , the blending of the first carbon black and the second carbon black was omitted, and 40.0 phr of the conductive carbon black used in Reference Example 1 was blended.
  • a light-blocking member for an optical apparatus in Comparative Example 1 was fabricated.
  • Example 2 Operation was performed as in Example 1 except using an application liquid for a light-blocking membrane CE 3 in which in the application liquid for a light-blocking membrane E 1 , the blending of the second carbon black was omitted, and the amount of the first carbon black blended was changed to 40.0 phr.
  • a light-blocking member for an optical apparatus in Comparative Example 3 was fabricated.
  • Example 2 Operation was performed as in Example 1 except using an application liquid for a light-blocking membrane CE 5 in which in the application liquid for a light-blocking membrane E 1 , the blending of the first carbon black was omitted, and the amount of the second carbon black blended was changed to 40.0 phr.
  • a light-blocking member for an optical apparatus in Comparative Example 5 was fabricated.
  • optical density was measured based on JIS-K7651: 1988 using an optical densitometer (TD-904: GretagMacbeth). In the measurement, a UV filter was used.
  • Optical density was divided by film thickness to calculate optical density per thickness of 1 ⁇ m ODt ( ⁇ m ⁇ 1 ).
  • the surface glossiness (specular glossiness) (%) of the light-blocking membrane surface at incidence and acceptance angles of 60° was measured in accordance with JIS-Z8741: 1997 using a digital variable angle glossmeter (UGV-5K: Suga Test Instruments Co., Ltd.). It is noted that the lower the glossiness is, the better the delustering properties are.
  • the static friction coefficient (s) and kinetic friction coefficient (k) of the light-blocking membrane were measured under the conditions of a load of 200 (g) and a speed of 100 (mm/min) in accordance with JIS-K7125: 1999, and each was evaluated according to the following criteria.
  • the optical density in terms of thickness (ODt) of the light-blocking membrane is as low as 0.51, and the total thickness is 10 ⁇ m (5 ⁇ m on one surface) in order to realize a light-blocking membrane having an optical density of 5 or more, and the light-blocking properties as basic performance are insufficient.
  • the slip properties are also poor.
  • Comparative Examples 3 and 4 carbon black having a larger average particle diameter than the carbon black used in Comparative Examples 1 and 2 is used.
  • the optical density in terms of thickness (ODt) is still low, and the light-blocking properties as basic performance cannot be said to be sufficient.
  • the surface glossiness deteriorates.
  • a matting agent is further blended in order to improve this deterioration of surface glossiness.
  • Comparative Example 4 One in which a matting agent is further blended in order to improve this deterioration of surface glossiness.
  • the surface glossiness can be kept low, but on the other hand the slip properties are greatly impaired.
  • Comparative Examples 5 and 6 carbon black having a smaller average particle diameter than the carbon black used in Comparative Examples 1 and 2 is used. It is seen that in the light-blocking members for optical apparatuses in these Comparative Examples 5 and 6, the optical density in terms of thickness (ODt) is high, and the light-blocking properties are excellent. However, in the light-blocking member for an optical apparatus in Comparative Example 5, as the carbon black is highly filled, the surface glossiness deteriorates significantly. One in which a matting agent is further blended in order to improve this deterioration of surface glossiness is Comparative Example 6. In the light-blocking member for an optical apparatus in this Comparative Example 6, due to the blending of the matting agent, the surface glossiness can be kept low, but on the other hand the slip properties are greatly impaired.
  • the optical density in terms of thickness (ODt) of the light-blocking membrane is high, and the light-blocking member for an optical apparatus adapts to film thinning, and at the same time the performance of light-blocking properties, surface glossiness, and slip properties is achieved at a high level.
  • ODt thickness
  • the use of a matting agent is essential for setting surface glossiness at 5.0 or less, but in the light-blocking member for an optical apparatus in Example 1 of the present invention, a surface glossiness of 3.0 is achieved without using a matting agent.
  • the following application liquid for a light-blocking membrane E 2 was applied to each of both surfaces of a polyester film having a thickness of 6 ⁇ m (K200: Mitsubishi Polyester Film Corporation) as a substrate by a bar coating method so that the thickness after drying was 3 ⁇ m, and dried. Then, heat treatment at 150° C. was performed using a circulating hot air dryer, and then UV irradiation treatment (accumulated amount of light: 1000 mJ/cm 2 ) was performed using a high pressure mercury lamp, to form a light-blocking membrane having a thickness of 3 ⁇ m on each of both surfaces of the substrate to fabricate a light-blocking member for an optical apparatus in Example 2.
  • Example 3 Operation was performed as in Example 2 except that in the application liquid for a light-blocking membrane E 2 , the amounts of the first and second carbon blacks blended were changed to 10.1 phr and 9.9 phr respectively. Thus, a light-blocking member for an optical apparatus in Example 3 was fabricated.
  • Example 4 Operation was performed as in Example 2 except that in the application liquid for a light-blocking membrane E 2 , the amounts of the first and second carbon blacks blended were changed to 15.1 phr and 14.9 phr respectively. Thus, a light-blocking member for an optical apparatus in Example 4 was fabricated.
  • the optical density in terms of thickness (ODt) of the light-blocking membrane is high, and the light-blocking members for optical apparatuses adapt to film thinning, and at the same time the performance of light-blocking properties, surface glossiness, and slip properties is achieved at a high level.
  • an optical density in terms of thickness (ODt) of 0.92 is achieved with an amount of carbon black filled of 15 phr.
  • an optical density in terms of thickness (ODt) of 1.00 is achieved with an amount of carbon black filled of 20 phr or more.
  • ODt optical density in terms of thickness
  • Comparative Examples 1 to 6 it is understood that in the light-blocking members for optical apparatuses in Examples 2 to 4 of the present invention, although the amount of carbon black used is reduced by 50% or more, excellent light-blocking properties can be realized.
  • the use of a matting agent is conventionally essential for setting surface glossiness at 5.0 or less, but in the light-blocking members for optical apparatuses in Examples 2 to 4 of the present invention, a surface glossiness of 2.5 to 3.0 is achieved without using a matting agent.
  • Example 5 Operation was performed as in Example 1 except that the blending ratio between the first black pigment and the second black pigment was 3:7, and the total amount of these was 40 phr. Thus, a light-blocking member for an optical apparatus in Example 5 was fabricated.
  • Example 6 Operation was performed as in Example 1 except that the blending ratio between the first black pigment and the second black pigment was 7:3, and the total amount of these was 40 phr. Thus, a light-blocking member for an optical apparatus in Example 6 was fabricated.
  • Example 7 Operation was performed as in Example 1 except that the blending ratio between the first black pigment and the second black pigment was 4:6, and the total amount of these was 30 phr. Thus, a light-blocking member for an optical apparatus in Example 7 was fabricated.
  • Example 8 Operation was performed as in Example 1 except that the blending ratio between the first black pigment and the second black pigment was 8:2, the total amount of these was 60 phr, and a light-blocking membrane having a thickness of 2 ⁇ m was formed on each of both surfaces of the substrate. Thus, a light-blocking member for an optical apparatus in Example 8 was fabricated.
  • the optical density in terms of thickness (ODt) of the light-blocking membrane is high, and the light-blocking members for optical apparatuses adapt to film thinning, and at the same time the performance of light-blocking properties, surface glossiness, and slip properties is achieved at a high level.
  • an optical density in terms of thickness (ODt) of 1.50 is achieved, and an optical density (OD) of 6.0 is achieved with a total film thickness of 4 ⁇ m (2 ⁇ m on one surface ⁇ 2), and not only are the light-blocking properties excellent, but especially significant film thinning is achieved.
  • the light-blocking member for an optical apparatus according to the present invention could adapt to a variety of optical apparatuses in which the degree of light-blocking properties required was different by the adjustment of the amount of the black pigments filled in the light-blocking membrane, its thickness, and the like.
  • the light-blocking member for an optical apparatus according to the present invention had high design flexibility in which the blending of other components was possible.
  • the light-blocking properties, basic performance, are especially excellent, and therefore adaptation to further film thinning is also possible.
  • the present invention can be widely and effectively utilized as a high-performance light-blocking member in the precision machine field, the semiconductor field, the optical apparatus field, and the like where lightness, thinness, shortness, and smallness are required.
  • the present invention can be especially effectively utilized as a light-blocking member for an inner wall surface or the like for an optical apparatus such as a high-performance single-lens reflex camera, a compact camera, a video camera, a cellular phone, or a projector, and as, for example, a shutter, a diaphragm member, or a lens unit.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Diaphragms For Cameras (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Shutters For Cameras (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Inorganic Chemistry (AREA)
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JP2020093472A (ja) * 2018-12-13 2020-06-18 スリーエム イノベイティブ プロパティズ カンパニー 熱伝導性成形体、その製造方法、構造体及び多層フィルム
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JP7386823B2 (ja) * 2021-02-16 2023-11-27 ソマール株式会社 液剤組成物、膜、及び膜を備える物品
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